Copolymers of dialkenyl arylphosphonates with vinyl acetate



Patented Nov. 9, 1948 COPOLYMERS F DIALKENYL ARYLPHOS- PHONATES WITH VINYL ACETATE Arthur Dock Fon Toy, Chicago, IlL, asslg'nor to Victor Chemical Works, a corporation of Illinois No Drawing. Application December 29, 1945, 7 Serial No. 638,456

18 Claims. (Cl. 154-4s) This invention relates to the formation of 00- polymers of at least one dialkenyl arylphosphonate with vinyl acetate.

In my copending application, Serial No. 625,459,

the amount of polymerization catalyst employed,

and by varying the polymerization time and temperature conditions.

In general the copolymers herein described are produced by mixing the liquid monomeric esters in the desired proportions and dissolving therein a small amount of catalyst and heating the mixture at a temperature generally just below that at which the most volatile of monomeric esters would boil ofi. Higher temperatures may be employed after the mass is partially polymerized or in case the polymerization reaction is carried out under pressure. The period o'f heating will depend upon the amount of catalyst employed and the degree of polymerization desired. For example, if the polymers are to be employed for impregnating fibrous materials in the production of laminated products, it is often desirable to arrest the polymerization while the polymers are in a viscous liquid state. In this partiallypolymerized state the resins may be advantageously applied with or without additional amounts of catalysts, and the polymerization to solid resins completed by further heating.

Organic peroxides such as acetyl peroxide, benzoyl peroxide, etc., are suitable catalysts for promoting the polymerization, and are generally employed in amounts ranging from 0.1% to about 5% by weight of the monomeric ester starting materials. f

The monomeric beta, gamma unsaturated dialkenyl arylphosphonate esters may be prepared in accordance with the process of the said Toy application Serial No. 625,459, filed October 29, 1945, which process comprises reacting beta, gamma unsaturated alcohols with arylphosphorus oxydichlorides in the presence of pyridine and separating the dialkenyl ester from the reaction mass. The resulting esters are liquid products which exhibit little or no tendency to polymerize except when mixed with a polymerization catalyst. Polymers of these esters are described in my co-pending application Serial No. 633,272, filed December 6, 1945 and require more severe polymerizin conditions than are required in forming the copolymers of the present invention. Further, the copolymers of the present invention are lighter colored, stronger, and cheaper to produce.

The copolymers of the present invention when fully polymerized are hard, tough, clear, substantially colorless solids which are iniusible and resistant to heat, dilute acids and alkalies. They are insoluble in organic liquids such as benzene, carbon tetrachloride, ether, acetone, alcohol, naphtha, gasoline, etc. They may be cast into various shapes by pouring the catalyzed monomeric mixed esters or partially polymerized vise cous liquids into suitable molds and heating to complete the polymerization. The solid resins may be ground and polished without difiiculty.

The following table illustrates a number of examples where the copolymers were produced by heating various mixtures of the monomeric esters with difierent amounts of polymerization catalysts .under different time and'temperature con dltions.

Q Demo 1 l lii'ti'ti' vinyl g y 32L023 Period A t t s a s o gt gggz fiy percgogte y G's g Tggl eer new. Properties oi Resin Products I p volulno volume figfifig Home o 100 0.01 70-73 15 4 5 in? and iliiklbbewa solid.

r gnme so 10 01 4: gairly [and 1and strong solid.

. ery so a so 10 0.01 70-13 58 1 m scans on 50 7 01 33. 5 Very soit gel.

70-73 19 Soft gel. 50 60 0. 05 70-73 38 Artgum-llkc solid.

80 +42 add. Strong. hard solid, water-white. 50 50 0.10 70-73 16.6 Hard artgum-liko, water-white solid. so so 0. 20 70-73 24 Very hard, strong, water-white, llama resistant 50 50 0.30 70 16 so id. so so 0. 40 70 Slightly yellow, hard, strong solid. 53 1% $8 73g 10 gee n crackgd.

. ecompose Diallyl Phenylphosphonate. 10 00 0. 00 lg strglrig, slightly soit, noniusible, flame resistant s l0 Water-white, artgurn-like solid.

60 :46) Strong iairly hard solid.

7 0 go w 50 m 60 Fairly hard. strong, water-white solid. 70 80 0. 20 80 19 Yellowlsh hard, stron solid. 90 10 0.20 70 24 Water-white, srtgum-l ke solid. 90 10 0. 20 80 19 Slightly yellow, clear, hard, strong solid. 100 0 0. 20 80 19 Eli htly lyellow, strong, herd solid.

70 30 0. 30 I 80 19 Yo ow, ard, strong solid. 90 10 0-30 80 8 D01.

- o e 7o 1o 60 40 Her strong, water-white solid. 70 so 0 80 16 Water-white srtgum-like solid.

' 30 Slightly yellow, clear, hard, strong solid. 7 70 80 0.60 70 16 Slightly yellow, hnrd, strong solid. Dingethsllyl Phenylphosso 60 0 67-70 D p onate.

30 70 0. 1 67-70 16 Slightly soit water-white stron solid. Diallyl Tolylphosvhonmu m to o. 2 1-10 16;? Slightly eutw, slightly 51m 5015i. Dlfnethnnyl Tolylphosphm an I 70 0.10 7-70 16% Axttggxrlrllzilre, water-white solid. Suriace hard and Drift 0.. as $8 az-zs 12g lifit 'ii"iiitrit i' a oro en 05- g y e ow s rong so so tsur ace. p y p to to 0.20 67-70 10 Clear, ellow, stronghard soli y From the above examples it' can be seen that by selecting suitable amounts of catalysts and reacting conditions satisfactory, strong, hard solid resins can be obtained with substantially all proportions of monomeric starting materials ranging 40 from 90% to 10% vinyl acetate and 10% to 90% of the dialkenyl arylphosphonate. However, from the standpoint of producing the most desirable type resins, it is preferred to employ proportions ranging from 70% to 30% vinyl acetate and 30% to 70% dialkenyl arylphosphonate, and from 0.1 to 0.3 grams of benzoyl peroxide per 10 cc. of the monomeric starting materials. Temperatures of 60 to 80 C. are shown to be satisfactory.

Examples in the above table using vinyl acetate alone produced unsatisfactory resins. As little as 1% of diallyl phenylphosphonate copolymerized with 99% of vinyl acetate will yield a solid resin product but for practical purposes a more satisfactory solid resin is obtained when at least 10% of the diallyl phenylphosphonate is employed. Such resins show improved flame resistance in proportion to the phosphonate component. A resin obtained from 70 parts vinyl acetate and 30 parts of the beta, gamma unsaturated dialkenyl arylphosphonate will burn in an applied flame but will extinguish itself after the external flame is withdrawn.

Laminated sheets of fiber glass and fabrics are prepared by impregnating the fibrous materials with liquid mixtures of beta, gamma unselturated dialkenyl arylphosphonates and vinyl acetate, containing from 1 to 3% benzoyl peroxide, pressing the impregnated layers together, and heating the mass in the compressed state at a temperature of 60 to 100 C. for a suflicient time to cause the impregnating liquids to polymerize, forming a strong, solid laminated sheet having a resin content of 30 to 60% by weight. The

amount of resin in the laminate may be varied by varying the viscosity of the original impreg-' nating liquids from that of the monomeric mixtures to the partially polymerized viscous liquid products.

The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom.

What I claim as new and desire to secure by Letters Patent is: v

1. A copolymer of 10 to 99% by volume of vinyl acetate and to 1% of a member of the class consisting oi diallyl and dimethallyl arylphosphonates.

2. The copolymer of claim 1 wherein the member of said class is a diallyl arylphosphonate.

3. The copolymer of claim 1 wherein the member of said class is a dimethallyl arylphosphonate.

4. The copolymer of claim 1 wherein the member of said class is diallyl phenylphosphonate.

5. The copolymer of claim 1 wherein the member of said class is diallyl chlorophenylphosphonate.

6. The copolymer of claim 1 wherein the member 01 said class is dimethallyl phenylphosphonate.

7. The copolymer of claim 1 wherein the amount of vinyl acetate is from 30 to 70% and the amount of the arylphosphonate is from 70 to 30%.

8. The method of making a resin which comprises mixing from 10 to 99% by volume of vinyl acetate and from 90 to 1% of a member of the class consisting of diallyl and dimethallylarylphosphonate. and heating at a temperature of from 60 C. to a temperature just below the temperature at which decomposition or distillation of the reactants and the resin products occurs. said reactants being heated in the presence 01 from 0.1 to 5.0% by weight of the starting esters of an organic peroxide catalyst.

9. The method of claim 8 wherein the member of said class is a diallyl arylphosphonate.

10. The method of claim 8 wherein the member of said class is a dimethallyl arylphosphonate.

11. The method of claim 8 wherein the member of said class is diallyl phenylphosphonate.

12. The method of claim 8 wherein the member of said class is a dimethallyl phenylphos-.

phonate. i

13. The method of claim 9 wherein said catalyst is benzoyl peroxide.

14. The method of claim 9 wherein the temperature is between 60 and 100 C.

15. The method of claim 9 wherein the temperature is between 60 and 80 C.

16. A composition of matter comprising a iam- REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Kosolapofi Nov. 20, 1945 Number 

